CA2052731A1 - Triazacyclohexane derivatives - Google Patents

Abstract

Triazacyclohexane derivatives Abstract Novel triazacyclohexane derivatives of formula I

(I), wherein R1 is hydrogen or C1-C4alkyl;
R2 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl or a radical -CH2B;
R3 is hydrogen; Cl-C10alkyl; C3-C6cycloalkyl; C1-C10alkyl substituted by from 1 to 12 radicals from the group halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9 halogen atoms, di-(C1-C4alkyl)amino and C1-C5alkoxycarbonyl;
C3-C6cycloalkyl substituted by from 1 to 4 C1-C4alkyl radicals or halogen atoms;C2-C8alkenyl or C2-C8alkynyl; C2-C8alkenyl or C2-C8alkynyl each of which is substituted by from 1 to 6 halogen atoms; phenyl; benzyl; or phenyl or benzyl each or which is substituted by from 1 to 3 ring substituents from the group halogen, C1-C4alkyl, C1-C4haloalkyl having from 1 to 9 halogen atoms, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9 halogen atoms, C1-C4alkylthio, nitro and cyano;

A is an unsubstituted or mono- to tetra-substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical that can have one or two substituents from the group C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl having from 1 to 3 halogen atoms, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1 to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and from one to four substituents from the group C1-C3alkyl, C1-C3alkoxy and halogen; and B is phenyl; cyanophenyl; nitrophenyl; halophenyl having from 1 to 3 halogen atoms;
phenyl substituted by C1-C3alkyl,C1-C3haloalkyl having from 1 to 7 halogen atoms, C1-C3alkoxy or by C1-C3haloalkoxy having from 1 to 7 halogen atoms; 3-pyridyl;
5-thiazolyl; 5-thiazolyl substituted by one or two substituents from the group Cl-C3-alkyl, C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxy, C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1 to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, halo-allylthio, halogen, cyano and nitro; or 3-pyridyl substituted by one or two radicals from the group C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3-haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or by from one to four radicals from the group C1-C3alkyl, C1-C3-alkoxy and halogen;

and salts thereof with inorganic acids, have valuable pesticidal properties. Compositions comprising those compounds, processes for the preparation thereof, and their use as pesticides, especially as insecticides and acaricides in agriculture, are described.

Description

~273~

PI/5-1 828]/A

Triazacvclohexane derivatives The present invention relates to novel substitwted 2-nîtroimino-1,3,5-triazacyclohexane derivatives, to processes for the preparation thereof, to pesticides that comprise those compounds, and to their use in thc control of pests.

The triazacyclohexane derivatives according to the invention correspond to formula I
Rl CH-A
N1~
02N-N =~2 3~N--R3 (I) I

wherein Rl is hydrogen or C1-C4alkyl;
R2 is hydrogen, Cl-C6aLkyl, C3-C6cycloalkyl or a radical -CH2B;
R3 is hydrogen; C1-ClOalkyl; C3-C6cycloalkyl; Cl-ClOalkyl substituted by f}om 1 to 12 radicals from the group halogen, hydroxy, Cl-C4alkoxy, Cl-C4haloalkoxy having from 1 to 9 halogen atoms, di-(Cl-C4alkyl)amino and Cl-Csalkoxycarbonyl;
C3-C6cycloalkyl substituted by from 1 to 4 Cl-C4alkyl radicals or halogen atoms;C2-C8alkenyl or C2-C8alkynyl; C2-C8alkenyl or C2-C8alkynyl each of which is substituted by from 1 to 6 halogen atoms; phenyl; benzyl; or phenyl or benzyl each of which is substituted by from l to 3 ring substituents ~rom the group halogen, Cl-C4alkyl, Cl-C4haloalkyl having from l to 9 halogen atoms, C~-C4alkoxy, Cl-C4haloalkoxy having from 1 to 9 halogen atoms, Cl-C4alkylthio, nitro alld cyallo;

A is an unsubstituted or mono- to tetra-substitllted arom;ltic or noll-arom.ltic, monocyclic or bicyclic he~erocyclic ra(lic;ll tll;lt can have one or two substituents from the group Cl-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl having from 1 to 3 halogen atoms, C2-C3il1kenyl, C2-C3alkynyl, 2~273 ~

C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, Cl-C3haloalkoxy having from 1 to 7 halogen atoms, Cl-C3alkylthio, Cl-C3haloalkylthio having from t to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and from one to four substituents from the group Cl-C3alkyl, Cl-C3alkoxy and halogen; and B is phenyl; eyanophenyl; nitrophenyl; halophenyl having from I to 3 halogen atoms;
phenyl substituted by Cl-C3alkyl, Cl-C3haloalkyl having from 1 to 7 halogen atoms, Cl-C3alkoxy or by Cl-C3haloalkoxy having from 1 to 7 halogen atoms; 3-pyridyl;
5-thiazolyl; 5-thiazolyl substituted by one or two substituents from the group Cl-C3alkyl, Cl-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, Cl-C3alkoxy, C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, Cl-C3haloalkoxy having from 1 to 7 halogen atoms, Cl-C3alkylthio, Cl-C3haloalkylthio having ~rom 1 to 7halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, halo-allylthio, halogen, cyano and nitro; or 3-pyridyl substituted by one or two radicals from the group Cl-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyelopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3-haloalkynyl each having from 1 to 4 halogen atoms, Cl-C3haloalkoxy having from 1to 7 halogen atoms, Cl-C3alkylthio, Cl-C3haloalkylthio having from 1 ts) 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, eyano and nitro, or by from one to four radieals from the group Cl-C3alkyl, Cl-C3alkoxy and halogen;

and salts thereof with inorganic acids.

The compounds of formula I aeeording to the invention also include the salts thereof with agrochemically tolerable inorganic acids. Examples of such acids are hydrochloric aci(l, hydrobromic aeid, sulfurie aeid, phosphorie aeid and nitric acid, and also acids hllving the same central atom and higher or lower degrees of oxidation, such as perchloric aci(l, nitrous acid or phosphorous acid.

The compounds of forrnula I can occur in talltomeric forms la or Ib whell the l-ldic.ll R2 is hydrogen:

~a273~

CH-A

02N-N =< ~N--R3 (la) X

CH-A
N ~
02N-NH~\ ~N--R3 (Ib).
N

The compounds of formula I can also occur as double-bond isomers with respect toN=C(2).

Formula I according to the invention is therefs)re to be understood as including formulae Ia and Ib and the double-bond isomers.

In the definition of forrnula I according to the invention, the individual generic terms are to be understood as having the following meanings:

The halogen atoms that come into consideration as substituents are fluorine and chlorine and also bromine and iodine, with fluorine, chlorine and bromine being preferred.
Halogen is here to be understood as being an independent substituent or part of a substituent, such as in haloalkyl, haloalkylthio, haloalkoxy, halocycloalkyl, haloalkenyl, haloalkynyl, haloallyloxy or haloallylthio. 'I'he alkyl, alkylthio, alkenyl, alkynyl and alkoxy radicals that come into consideration as substit~lents can be straight-chain or branched. There may be mentioned as examples of such alkyl radicals methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-b~ltyl. Suitable alkoxy radicllls are inter alia: methoxy, ethoxy, propoxy, isopropoxy, or butoxy and its isomers. Alkylthio is, for example, methylthio, ethylthio, isopropylthio, propylthio or the isomers of butyltllio.
If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups that come hlto consider,ltion as substituents are substituted by halogen, they may be only parti.llly h.llogenace(l or altern,l-tively per-halogenated. Halogen, alkyl and alicoxy here have the definitions given above.
Examples of the alkyl elements of those groups are methyl substitute(l fiom one to three 7 3 ~

times by fluorine, chlorine and/or by bromine, for example CHr2 or CF3; ethyl substiluted from one to five times by fluorine, chlorine and/or by bromine, for example CH2CF3, CF2CF3, CF2CCI3, CF2CHC12, CF2CHF2, CF2CFC12, CF2CHBr2, CF2CHCl~, CF2CHBrF
or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine ancVor by bromine, for example CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or one of its isomers substituted from one to nine times by fluorine, chlorine and/or by bromine, for example CF(CF3)C~IFCF3 or CH2(CF2)2CF3; 2-chloro-cyclopropyl or 2,2-difluorocyclopropyl; 2,2-difluorovinyl, 2,2-dichlorovinyl, 2-chloroalkyl, 2,3-dichlorovinyl or 2,3-dibromovinyl.

If the alkyl, alkoxy or cycloalkyl groups defined are substituted by other substituents, they may be mono- or poly-substituted by identical or different substituents selected from those listed. Preferably, one or two other substituents are present in the substituted groups. The cycloalkyl radicals that come into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Alkenyl and alkynyl groups contain one unsaturated carbon-carbon bond. Typical examples are allyl, methallyl or prop~Lrgyl, but also vinyl and ethynyl. The double or triple bonds in allyloxy, propargyloxy, allylthio or propargylthio are separated from the point of linkage to the hetero atom (O or S) preferably by a saturated carbon atom.

Of the compounds of formula I defined above, prominence is to be given to those wherein the radical R3 is Cs-CIOalkyl; C3-C6cycloalkyl; C1-ClOalkyl substituted by from 1 to 12 radicals from the group halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9halogen atoms, di-(C1-C4alkyl)amino and Cl-Csalkoxycarbonyl; C3-C6cycloalkyl substituted by from 1 to 4 Cl-C4alkyl radicals or halogen atoms; C2-C8alkenyl orC2-C8alkynyl; C2-C8alkenyl or C2-C8alkynyl each of which is substituted by from 1 to 6 halogen atoms; phenyl; benzyl; or phenyl or benzyl each of which is substituted by from 1 to 3 ring substituents from the group halogen, Cl-('4alkyl, Cl-C4hil10alkyl having from 1 to 9 halogen atoms, Cl-C4ialkoxy, Cl-C4haloalkoxy hiaving from 1 to 9 halogen atoms, Cl-C4alkylthio, nitro and cyiano; an(l Rl, R2 and A are as defil-e(l above.

Of special importance according to the invention are also those compouncls of formuhl I
wherein the heterocyclic radical A is unsat-lrated, is bonded v a a carbon atom to the radical of the molecule of the compound of formula I and contains at least one nitrogen 3 ~

atom; those compounds wherein the heterocyclic radical A is unsaturated, is bonded via a carbon alom to the radical of the molecule of the compound of formula I and contains from one to three hetero atoms from the group oxygen, sulfur and nitrogen, not more than one oxygen or sulfur atom being present; and those compounds wherein the heterocyclic radical A contains from one to three hetero atoms from the group oxygen, sulfllr and nitrogen, of which one hetero atom is always nitrogen, not more than one oxygen atom or sulfur atom being present.

The ring systems covered by the derlnition of the heterocyclic radical A are signific.lrlt as regards the biological activity of the compounds of formula I according to the invention.
These ring systems contain at least one hetero atom as ring member, that is to say at least one of the atoms forming the basic cyclic structure is other than carbon. In principle, all atoms of the periodic system of the elements are capable of acting as ring members, provided they are able to form at least two covalent bonds. The heterocyclic radical is preferably unsaturated and bonded to the basic structure of formula I via a carbon atom as ring member. Unsaturated ring systems of the definition A contain one or more double bonds; such ring systems are preferably polyunsaturated and are generally of aromatic nature. Preference is given to ring systems that contain at least one nitrogen atom as hetero atom. Such rings of the definition A usually contain from one to three hetero atoms from the group oxygen, sulfur and nitrogen, not more than one oxygen or sulfur atom being present. Preference is given to ring systems of the definition of A wherein the heterocyclic radical A contains from one to three hetero atoms from the group oxygen, sulfur and nitrogen, of which one hetero atom is always nitrogen, not more than one oxygen atom or sulfur atom being present. Examples of heterocycles of definition A according to the invention are to be found especially in the following group of basic structures:

o~ o~ s 3 o~ s ~ S ~ 5 3 S d~ N
E E

O ~ S~o3 S~J o 3 o~ 3 ' 0~ S Jl S ~3 o~N 3 o~ o i s ~;3 S ~ N 3 E E

N~\N N~ 3, D~ ~N ~ N~ 3 sd~oJ o~o o oo o-- o~s ~ ~N S~ N~ 3 ~ ~N ~

E E E
s ~ o3 s ~o J s ~o-- s J\ s 3 s ~ s J

S ~ S ~S ~1 N 3 S ~ N S ~ N
E E E

2 ~ ~ 2 1 3 :l N ~3 N~;;3 [~3 ~3 1~3 ,N0~3 ' N~3 , Nf~3 .

N ~ ~N ~3 ~ N ~ N . ~ N

N 1~ N N
~N~ ~N~ ~N ~ N N . N~ ~N ~ N~ J

ND--IN~

O O O Y S

~N ~~N . ~, ~3 ~, S S Y

N~ N~ N--~ 1 ~N~
I~NJ~N JJ O J~N ~ I~ S J~`N ~ N J~N

~S /~N~I Nrl~3 N~N ~3 N~N ~ N~N ~ N~N

o~N O~NlS O~N I S~N

N~\N N~\N

S ~Nl~l S ~\N~ ~3 In the above formulae, E is C1-C3alkyl and Y is hydrogen, C1-C3alkyl or cyclopropyl.

The heterocycles A listed as examples above can be unsubstituted or, depending on the number of substituents possible in the ring sys~em, can carry up to four of the substituents indicated under formula I. Preferab]y, these heterocycles carry from one to three substituents fr~m the group halogen, Ci-C3alkyl, Cl-C3haloalkyl and Cl-C3haloalkoxy each having from 1 to 7 halogen atoms, and Cl-C3aLkoxy. Especially preferred hetero-cycles A are pyridyl radicals or thiazolyl radicals, for example 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-4-yl, 1-oxopyrid-3-yl, 1-oxo-2-halopyrid-5-yl and 1 -oxo-2,3-dihalopyrid-5-yl.

In the compounds of formula I, the radical B is preferably a phenyl, pyridyl or thiazolyl radical that can be unsubstituted or substituted by one or two radicals from the group halogen, Cl-C3alkyl, Cl-C3haloalkyl and Cl-C3h,lloalkoxy each having from I to 7halogen atoms, and Cl-C3alkoxy.

Of the compounds of fonnula 1, prominence is to be given, on account of their biological properties, to those compounds wherein Rl is hydrogen, R2 is mcthyl, ethyl or cyclopropyl, and A is pyridyl, l-oxopyridyl or thiazolyl, or is pyridyl. l-oxopyri(lyl or thiazolyl each of which is substituted by frs)m one to three substituents from tl-e group halogen, Cl-C3alkyl, Cl-C3haloalkyl and Cl-C31-aloalkoxy e.lch having from 1 to 7 ~5~7cl~

halogen atoms, and Cl-C3alkoxy. Within this meaning, also of interest are those compounds of formula I wherein a) Rlis hydrogen; and/or b) R2 is methyl; and/or c) R3is cl-c3alkyl~ cyclopropyl, cyclohexyl, phenyl, benzyl or the radical -CH2-COO-CH3.

Also of intercst in accordance with the invention are those classes of compo-1nd of formula I wherein R3 is benzyl or phenyl each of which is substituted by from I to 3 ring substituents from the group fluorine, chlorine, bromine, Cl-C2alkyl, Cl-C2haloalkyl, Cl-C2alkoxy, Cl-C2alkylthio, nitro and cyano;
R3 is Cl-C6alkyl substituted by a hydroxy group;
R3 is Cl-C6alkyl substituted by a Cl-Csalkoxycarbonyl group;
R3 is-CH2CH2F,-CH2CH2Br,-CH2CH2CH2Cl,-CH2CH2CH2Br or -CH2CHClCH2CH2CH2Cl;
R3 is-CH2CH20 CH3,-CH2CH2CH2-O-CH2CH3,-CH(CH3)CH2-O-CH3, -CH2CH(OCH3)2, -cH2cH2-N(cH2cH3)2~ -CH2-CI~2CH2-N(CH3)2 or -CH2CH2CH2-N(CH2CH3)2;
R3 is c4-c6cycloalkyl that is unsubstituted or substituted by one or two Cl-C4alkyl radicals;
R3 is cyclopentyl or cyclohexyl;
R3 is c3-c6cycloalkyl substituted by one or two methyl groups;
A is 2-chlorothiazol-4-yl, 2,3-dichloropyrid-S-yl, l-oxopyrid-3-yl or l-oxo-2-chloropyrid-5-yl; R2 is methyl and R3iscyclopropyl~-cH
-CH2CH(OCH3)2 or -CH2CH2N(CH3)2;
A is 2-chlorothiazol-4-yl;
A is 2-chloropyrid-S-yl; or A is 2-chloropyrid-S-yl, 2,3-dichloropyrid-S-yl, 2-chlorothiazol-4-yl, 1-oxopyrid-3-yl or l-oxo-2-chloropyrid-5-yl; Rlis hydrogen; R2 is methyl; and R3 is n-propyl.
The compounds of formula I according to the invention can be preparc~l by, ior examplc, a) reacting a compound of formula Il ~5~73~

~o -Rl I

NH--CH--A
02N--N =< (II) with forrnaldehyde, or paraformaldehyde, and a compound of forrnula Ill H2N-R3 (III);
or b) reacting a compound of formula IV

02N-N =~ ~N--R3 ~IV) N

with a compound of formula V

l1 X--CH--A (V);
or c) for the preparation of a compound of ~ormula I wherein R2 is other than hydrogen, reacting a resulting compound of formul.l I wherein R2 is hydrogen with il compou of forrmula VI

Y-R2 (Vl);
and, if desired, converting a resultillg compoulld of fomlula I into a salt thereof in a 7'~ ~

manner known ~ se; R1, R2, R3 and A in formulae II to VI being as defined above, X
being halogen and Y being a leaving group. There may come into consideration as leaving groups X and Y, for example: halogen, preferably chlorine, bromine or iodine, or sulfonic acid radicals, such as alkanesulfonic acid radicals, mesylate or tosylate.

Variant a) of the above process according to the invention is advantageously carried out under normal pressure, but may also be carried owt under clevatcd pressure, in an inert solvent and at temperatures of from 0C to +140C, especially from +20C to +12()C.
Suitable solvents are especially alcohols, such as mcthanol, ethanol and yropanol, ~mcl also water. Other suitable solvents are, for example, aromatic hydrocarbons, such as benzene, toluene and xylene; ethers, such as tetrahydrofuran, dioxane and diethyl ether; halogenatecl hydrocarbons, such as methylene chloride, chloroforrn, carbon tetrachloride and chlorobenzene, and other solvents that do not impair the reaction. The solvents may also be used as mixtures. The reaction may be carried out with the addition of an acid catalyst, such as HCl, H2SO4, or a sulfonic acid, such as p-toluenesulfonic acid. The resulting water of reaction can, where necessary, be removed by means of a water separator or by the addition of a molecular sieve.

The above-mentioned process variants b) and c) can preferably be carried out under normal or slightly elevated pressure znd in the presence of preferably aprotic solvents or diluents. Suitable solvents or diluents are, for example, ethers and ethereai compounds, such as diethyl ether, dipropyl ether, dibutyl ether~ dioxane, dimethoxyethane and tetrahydrofuran; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene;
nitriles, such as acetonitrile or propionitrile; dimethyl sulfoxide and dimethylformamide.
The processes are generally carried out at a temperature of from -20 to +140C, preferably from 0 to +120"C, preferably in the presence of a base. Examples of suitable bases arc carbonates, such as sodium and potassium carbonate. Hydridcs, such as sodiurn hydridc, potassium hydride and calcium hydride, can also be used as bascs.

The starting materials of formulae II, III, V and Vl arc kllown or cal- bc plcp;llcd analogously to known processes.

The 2-nitroguanidine derivatives uscd as starting m;lteri;lls of formul;l Il, all(l the preparation thereof, are known from EP Patent Applications 375 9()7 an~l 376 279. The primary amines of forrnula III are products that are readily avail;lbîe commercially.

2 ~ ~ ~ rt 3 ~

The 2-nitroimino- 1,3,5-eriazoles of folmula IV, to which the present invention also relates, are obtainable by reacting a 2-nitroguanidine of formula VII

O2N N=< (VII) NH
l2 with formaldehyde, or paraformaldehyde, and a compound of formula III

H2N-R3 (III), R2 and R3 in forrnulae VII and III being as defined above. The reaction conditions for this process are the same as those for process variant a) above for the preparation of the compounds of formula I. The compounds of formula IV are novel with the exception of 2-nitroimino-5-methyl-1,3,5-eriazacyclohexane (EP Patent Application 0 386 565) and 2-nitroimino-1,3,5-triazacyclohexane (US-PS 4 937 340). The nitroguanidines of formula VII are known (see US-PS 4 804 780 and 4 221 802) or can be prepared in analogous manner.

A large number of compounds of formula V are known (see, for example, EP Patent Applications 375 907 and 376 279). There are preferred as starting materials those compounds of formula V wherein X is chlorine.

Similarly, a large number of compounds of forrnula VI are known. They are products thae are commercially available or that are readily obtainable analogously to known processes.
The leaving group Y in those compounds is preferably a halogen atom, especially chlorine.

It is already known that some open-chained 2-nitroguani(line dcrivatives have pesticidal properties (see, for example, EP Patent Applications 0 375 907 and 0 376 279). I-lowever, pesticidal heterocyclic compounds based on a nieroguallidine stmcture are also known.
For example, EP Patent Applicatiol1s 0 192 060 and 0 259 738 dcscribe 2-nieroiminopyrimidine derivatives having insecticidal activity. Furtllermore, in US-PS 4 937 340, 2-nitroimino-1,3,5-triazacyclohexane and other corresponding ~ ~3 ~i ~ ,Y 3 derivatives containing nitro groups are proposed as additives for explosives. Insecticidal compounds of the type according to the invention are propose~ in EP Patent Application 0 386 565, the compounds of formula I according to the invention being partially covered by the broad scope of the claims of this EP Patent Application.

Surprisingly, it has been found that the compouncls of formula I according to the invention are valuable active ingredients in pest control while being well tolerated by warm-blooded animals, rlsh and plants. The compollnds according to the invention can be uscd especially against insects that occur on us~ful plants and ornamentals in agriculture, espe-cially in cotton, vegetable and fruit crops, in forestry, in the protection of stored ~oods and material stocks, and also in the hygiene sector, especially on domestic animals and productive livestock. The compounds are effective especially against plant-destructive sucking insects, especially against aphids and cicadas. They are effective against all or individual development stages of normally sensitive and also resistant species. Their action may manifest itself in the death of the pests immediately or only at a later date, for example at moulting, or in reduced oviposition and/or a reduced hatching rate. The above-mentioned pests include:
of the order Lepidoptera, for example Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., E~usseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp.,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia Iycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, I,ymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassic.le, Mallduca scxta, Operophtera spp., Ostrinia nubilalis, Pamrnene spp., Pandemis spp., Pallolis nammea, Pectillophora gossypiella, Phthorimaea operc-llclla, Pieris rap.le, Pieris spp., Plutcll.l xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparg.lnothis spp., Spodol)tera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichopl~lsi.l ni al-d Ypollolllcllta spp.;
of the order Coleoptera, for examplc Agriotes spp., Anthonomus spp., Atom;lria line~uris, Ch.lctocllema libialis, Cos-nopolitcs spp., Curculio spp., Dermestes spp., Diabrotic.l spp., Epilaclln,l spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrlls spp., Melolontll,l spp., Orycaepllil~ls spp., 7 ~ ~

Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scara-beidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; of the order Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;
of the order Isoptera, for example Reticulitermes spp.; of the order Psocoptera, for example Liposcelis spp.; of the order Anoplura, for example Haematopinus spp., Linognathus spp., Pedictllus spp., Pemphigus spp. an(l Phylloxera spp.; of the or(ler Mallophaga, ~or example Damalinea spp. and Trichodectes spp.;
of the order Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothrips spp., T hrips palmi, Thrips tabaci and Scirtothrips aurantii;
of the order Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;
of the order Homoptera, for example Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus diclyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., L.aodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;
of the order Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpini.l polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis sPI).
and Vespa spp.;
of the order Diptera, for example Aedes spp., Antherigona soccata, Bibio hortllhll1lls~ Callipllor.l crytllroccpll.ll.l, Ccr.ltitis spp., Chrysomyia spp., Culex spp., C~lterebra spp., Dacus spp., Drosopllila mel,lnog.lster, Fannia spp., Gastropl1ilus spp., Glossina spp., llypodcrm.l spp., Ilyppobosc,l spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orscolia spp., Oscinella frit, Pegomyia hyoscyalni, Phorbi.l spp, Rh.lgoletis pomonella, Sciara spp., 7 ~ ~

Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
of the order Siphonaptera, for example Ceratophyllus spp., Xenopsylla cheopis;
of the order Acarina, for example Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus lat~ls, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; and of the order Thysanura, for example Lepisma saccharina.

The good pesticidal activity of the compounds of formula I according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests.

The activity of the compounds of the invention and of the compositis)ns comprising them can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides. Examples of suitable additives include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives thereof, forrnamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.

The compounds of forrnula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wcttable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances. As with the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compounds of formula I are also suitable for use in the treatment of seed. For this purpose it is possible either to treat or dress the seed with the active ingrediellt or with a formu-lation comprising the active ingredient before sowing, or to apply the active ingredient into the seed furrow at the time of sowing.

The formulations, i.e. the compositions, preparations or mixtures comprising the 2 ~ 3 ~

compound (active ingredient) of fomlula I, or combinations of those compounds wilh other insec-icides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the C8 to Cl2 fractions of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols such as ethanol, propanol or butanol, and glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl ormonoethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol,strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylforrnamide, or water, vegetable oils such as rape oil, castor oil, coconut oil or soybean oil; and, where appropriate, silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral ~Illers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of granulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of forrnula I to be formul.lted, or of the combinations of those compounds with other insecticides or acaricides, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants havillg good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfact.mts.

Both so-called water-soluble soaps and water-solllble synthetic sulface-active co~ )0llnds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alk.lline earth metal salts or unsllbstitllte~l or substituted ammonium salts of higher fatty acids (C1o-C22), e.g. the sodillm or potassium 7 ~ :~

salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g.
from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline e~rth metal salts or unsubstituted or substitute-1 arnmonium salts ancl gencrally contain a C8-C22alkyl radical, which also includes the alkyl moiety of acyl raclicals, e.Lg the soclium or calcium salt of lignosulfonic acicl, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolarnine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms ir. the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups anci 10 to 10() propylene glycol ether groups. These cornpounds usually contain 1 to 5 ethylene glycol units pcr propylene glycol unit.

Representative examples of non-ionic surf.lct.lnts are nonylpllcnolpolyctlloxyetl~ lols~
castor oil polyglycol ethers, polypropylene/polycthylelle oxicle aciclllcts, tributylpilelloxy-polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxycth;lnc)l. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylcne sorbitan triolcate, are also suitable non-ionic surfactants.

~273~

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in formulation technology are describcd, for example, in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., (:~len Rock, NJ, USA, 1988", H. Stache, "I'ensid~Taschenbuch", 2nd edition, 1:~. Hanser Verlag, Munich, Vienna, 1981, M. and J. Ash, "Encyclopedia of ~urfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

The pesticidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combinations of that compound with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant. Whereas commercial products will preferably be formulated as concen-trates, the end user will norrnally employ dilute formulations comprising considerably lower active ingredient concentrations. Typical application concentrations are from 0.1 to 1000 ppm, pre~erably from 0.1 to 500 ppm. The rates of application per hectare are generally from 1 to 1000 g of active ingredient per hectare, preferably from 25 to 500 g/ha.

Preferred formulations have espccially the following compositions (tlllc)-lgllollt, percentages are by weight), active ingrcdicnt being understood as mc,l~ g a compoun(l of formula I:

Emulsifiable concentrates:
active ingredient: 1 to 90 %, prefer,lbly 5 to 20 /0 surface-active agent: 1 to 3() %, preferably 10 lO 2() %
liquid carrier: 5 to 94 %, prefcrably 70 to X5 %

~27~

Dusts:
active ingredient: 0.1 to 10 %, preferably 0.1 to 1 %
solid carrier: 9~.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates:
active ingredient: 5 to 75 %, preferably 10 to S() %
water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to ~0 %, preferably 2 to 30 %

Wettable powders:
active ingredient: 0.5 to 90 %, preferably 1 to 80 %
surface-active agent: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules:
active ingredient: ~.5 to 30 %, preferably 3 to 15 %
solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The compositions may also comprise further auxiliaries such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti-foams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

The following Examples serve to illustrate the invention, but do not limit the invention.

Example l_(~aration of starting materials of formula IV):
a) Preparation of 2-nitroimino-S-methyl-1~3,5-tria~acyclohexane.
~ mixture of 26.0 g of 2-nitroguanidine, 31.1 ml of an 8M solution of methylamine in ethanol, 38 ml of a 37 % solution of formaldehyde in water, and 1()() ml of ethallol is heated at 50C for 2 hours and then filtered. The crystals whicll have been f;ltered off ale washed three times with 20 ml of ethanol each time and then drie(l, yieIding the title cornpound, m.p. 173-175C, of the formul.l 2 ~ ~ 2 ~ ~1 N~
02N-N=< N--CH3 ~compoundno. 2.001).
N
H

b) Preparation of 1-methyl-2-nitroimino-S-n-pr~y 1 ~3,5-triazacvclohexane:
A mixture of 17.1 g of 1-methyl-2-nitroguanidine, 12.0 ml of n-propylamine, 22.0 ml of a 37 % solution of formaldehyde in water, and 40 ml of ethanol is heate(l ae 50C for 4 hours. A further 7.0 ml of n-propylamine and 13.0 ml of a 37 % solution of formaldehyde in water are then added. After stilTing at 50C for 2 hours, the reaction mixture is concentrated by evaporation in vacuo and the crystals which have separated out are stirred with ether, yielding 26.9 g of the title compound, m.p. 84-86C, of the formula H

N ~
02N-N =( N--C3H7 (n) (compound no. 2.011).

c) Preparation of 1-methyl-2-nitroin-1ino-5-phem/1-1,3,5-~iazacyclohexane:
Three drops of concentrated hydrochloric acid are added to a mixture of 2.36 g of 1-methyl-2-nitroguanidine, 2.11 ml of aniline and 1.80 g of paraformaldehyde in 30 ml of toluene, and the mixture is then boiled in a water separator for 6 hours. The reaction mixture is then concentrated by evaporation in vacuo and the resulting crude product is recrystallised from methanol, yielding the title compound, m.p. 169- 172C, Or the formula N
N

02N-N :=~ N--~ (compo~lnd no. 2.()44).

C~13 The following compounds of formula IV c~m be prepared as inclicatc(l above:

7 3 ~

Comp. R2 R3 Phys. data No.

2.001 H Cl-I3 m.p. 173-175C
2.002 H -C2E-ls m.p. 181-182C
2.003 H -C3H7(n) 2.004 H CH(CH3)2 2.005 H ~1 m.p. 225-227C

2.006 H ~3 2.007 2.008 H --CH2 ~
2.009 CH3 -CH3 m.p. 134-135C
2.010 ~H3 -C2Hs m.p. 112C
2.011 CH3 -C3H7(n) m.p. 84-86C
2.012 CH3 -CH2(C~I3)2 m.p. 154C
2.013 CH3 ~ m.p. 177C

2.014 CH3 {~3 m.p. 103-104C
2.015 S~H3 -Cfills m.p. 169-172C
2.016 CH3 --CH2 ~ m.p. 161-163C

2.017 -C2Hs -CH3 2.018 -C2l-Is -C2H5 m.p. 95-96C
2.019 -C2Hs -C3H7(n) 2.020 -C2Hs -CH(CH3)2 7 3 :~

Comp. No. R2 R3 Phys. d~t~
-2.021 -C2Hs -2.022 -C2H

2.023 -C2H

2.024 -C2Hs - CH

2.025 ~ -C~13 2.026 ~ -C2Hs m.p.138-139C
2.027 ~ -C3H7~n) 2.028 ~ -CH(CH3)2 2.029 2.030 2.031 2.032 ~ -C~12 ~

2.033 - CH2 ~ -Ci 13 m.p. l()')-111C

2.034 - CH2 ~ -C2l-1s 7 ~ ~

Comp. No. R2 R3 Phys. data 2.035 --CH2 ~ -C3H7(n) 2.036 --CH2 ~ CH(CH3)2 2.037 --CH2 ~3 ~

2.038 --CH2 ~ {~>

2.039 --CH

2.040 --CH2 ~ --CH
2.041 H -CH2-COOCH3 2.042 -CH3 -CH2-COOCH3 2.043 ~ -CH2-COOCH3 2.044 -CH3 ~ m.p. 169-172C
2.045 -CH3 -CH2CF3 2.046 -CH3 -CH2CH2E~`
2.047 -CH3 -CH2CH2Br 2.048 -CH3 -CH2CH2C~-l2cl 2.049 -CH3 -CH2CH2CI 12Br 2.050 -Cl 13 -CH2CH2CI
2.051 -CH3 -Cl-12CH(CI)CH2CH2CI I~CI
2.0S2 -Cl-13 -CE-12CH2OH m.p. 121-123C
2.053 -CH3 -CH2CH2CI-I~OH
2.054 -CH3 -C~-12CH2CH2CH2OH m.p. X 1 -83C

2~27~

Comp.No. R2 R3 Phys.d~ta 2.055 -C~13 -CH2CH2Cl-I2c~-l2cH2OH
2.056 -CH3 -CH(CH3)CH30H
2.057 -CH3 -CH(C211s)CH2OH
2.058 -CH3 -CH2CH(CH3)OH
2.059 -CH3 -CH2CH(OH)CI-12OH
2.060 -CH3 -CH(CH2OH)2 2.061 -C~I3 -CH2CH2OCH3 2.062 -CH3 -CH2CH2CH2OC2Hs 2.063 -CH3 -CH(CH3)CH2OCH3 2.064 -CH3 -CH2CH(OCH3)2 2.065 -CH3 -CH2CH(OC2Hs)2 2.066 -CH3 -CH2CH2N(CH3)2 2.067 -c~3 -CH2CH2N(C2Hs)2 2.068 -CH3 -CH2CH2CH2N(CH3)2 2.069 -CH3 -CH2CH2CH2N(C2Hs)2 2.070 -CH3 -CH2COOC2Hs 2.071 -CH3 CH2CH2COOC2Hs m.p.llO-112C
2.072 -CH3 -CH(CH3)CH2C~OC2~s 2.073 -CH3 -CH(CH2OH)COOCH3 2.074 -CH3 ~

2.075 -CH3 ~ CH3 m.p.lsl-ls3oc(cisi~o~ r) m.p.l38-14()~C(trl~sisomer) 2.076 -CH3 ~ CH3 >~
2.077 -CH3 ~ H>

Comp. No. R2 _R3 Phys. data 2.078 -C~13 -CH2-CH=CH2 m.p. S3-55C
2.079 -CH3 ~ - Cl 2.080 -CH3 ~F m.p. 170-173C

2.081 -CH3 ~OCH3 m.p. 174-176C

2.082 ~3 m.p.195-197C

2.083 -CH3 ~NO2 m.p.230C

2.084 -CH3 ~ CN m.p.222-226C

2.085 -CH3 ~CF3 m.p. 163-166C

2.086 -CH3 ~

SC~13 2.087 -CH

2.088 -CH

2~273~

Comp. No. R2 R3 Phys. data _ NC
2.089 -CH3 ~3 2.090 -CH3-CH2 ~ No2 m.p. 235-238C

2.091 -CH3-CH2 ~ F m.p. 143-145C

2.092 -CH3-CH2 ~3OCH3 m.p. 132-134C

2.093 -CH3-CH2 ~ Cl m.p. 160- 162C

2.094 -CH3-CH2 ~ CH3 m.p. 161 - 163 C

2.095 -C~3-CH2 ~ CF3 m.p. 160- 162C

2.096 CH3-CH2 ~3 2.097 -CH3-CH2 ~3 F

2.098 -Cl13 -CH2 ~ F

20~ii2r~3~

Comp. No. R2 R3 Phys. data CN
2.099 -C~13 -C~l Example 2:
a) Preparation of 1-(2-chloropyrid-5-ylmethyl)-2-nitroimino-S-ethyl-1~3 5-triazacvclohexane:
A mixture of 1.15 g of 1-(2-chloropyrid-5-ylmethyl)-2-nitroguanidine, 0.75 ml of a 37 %
solution of formaldehyde in water, 0.32 ml of a 70 % solution of ethylamine in water, and 5 ml of ethanol is heated at 50C for 4 hours. The reaction mixture is then concentrated by evaporation in vacuo, the residue is suspended in 20 ml of ethanol, and the resulting crystals are filtered off, yielding the title compound, m.p. 125-126C, of the fs)rmula CH2~ N
~--CI
02N-N=~ N--C2H5 (compoundno. 1.001).
H

b) Preparation of 1-(2-chloropyricl~lmethyl)-2-nitroimino-5-cyclop 1.3~S- riazacyclohexane:
A mixture of 2.96 g of 2-nitroimino-S-cyclopropyl-1,3,5-triazacyclohexanc7 2.59 g of 2-chloro-5-chloromethylpyridine and 2.43 g of potassium carbonate in 60 ml of acetonitrile is heated under reflux for 16 hours. Thc resulting rcaction mixture is filtercd, the filtrate is concentrated by evayoratioll in vacuo and the residue that forms is chromatographed on silica gel with dichlorometh.me/ethyl acetate (1:1), yieldin,g the title compound, m.p. 125-127C, of the formula CH2~ N
N~ ~CI
02N-N=< ~ ~1 (compound no. 1.003).
H

c) Prepalation of 1-~chloropvrid-5-ylrnethyl)-2-nitroimino-3-n ethYI-5-n-proPy -1 3,5-triazacyclohexane:
A mixture of 20.1 g of 1-methyl-2-nitroimino-5-n-propyl-1,3,5-triazacyclohexane, 16.2 g of 2-chloro-5-chloromethylpyridine, 0.17 g of caesiwn chloride and 27.7 g of potassium carbonate in 150 ml of DMF*) is heated at 110C for 9 hours and then filtered over Celite.
The filtrate is concentrated by evaporation in vacuo. The resulting crude product is dissolved in 200 ml of dichloromethane and washed with 100 ml of water and 100 ml of saturated sodium chloride solution, dried over magnesium suifate and then concentrated by evaporation. The residue is recrystallised from ethyl acetate, yielding the title compound, m.p. 137-138C, of the formula CH2 ~ N
~CI
N ~
02N-N =~ N--C3H7(n) (compound no. 1.009).
N

~)dimethylformamide d) Preparation of 1-(2-chloropyrid-5-y~ ethyl)-2-nitroimino-3,5-_(~
1 ~3,5-triazacvclohexane:
0.30 g of sodium hydride (80 % in white oil) is adcled to a solution of 3.12 g of 1-(2-chloropyrid-5-ylmethyl)-2-nitroimino-5-1l-propyl-1,3,5-tri.lz.lcyclollcx.lne in 5() ml of acetonitrile. After stirring the reaction mixture at room tempcratllrc for 3 hours, 1.8 ml of n-propyl iodide are added, and the reaction mixture is thel- stirrcd at room temperat-lre for 16 hours and at 80C for 2 hours. The residue obtained after concentr.l~ion by evllpor.ltior in vacuo is taken up in 100 ml of ethyl acet.lte~ washed with 50 ml of saturatecl sodilln-chloride solution, dried over magnesium sulf.lte and ag.lin concentrated by evapor.ltion.

2~5273~

The crystals obtained as residue are recrystallised at 0C from ethyl acetate, yielding the title compound, m.p. 112-113C, of the formula CH2 ~ N
~CI

02N-Na~ N--C3H7(n) (compound no. 1.025).

C3H7(n) The following compounds of formula I can be prepared as indicated above:

2~ J31 Comp. A Rl R2 R3 Phys. data No.

1.001 ~ ~ H H -C2~Is m.p. 125-126C

1.002 ,¢~1' H H -C3H7(n) m.p. 115-117C

1.003 ,¢~1' H H ~ m.p. 125-127C

1.004 ,¢~1' H H {3 m.p. 150-151C

1.005 ,¢~J~ H H ~ m.p. 143-145C

1.006 ,¢;~ H H -CH2~ m.p. 108-110C

1.007 ,¢~/ H CH3 -c~3 amorphous mass 1.008 ,¢;~ H CH3 -C2lIs m.p. 124-125C

1.009 ,¢~1' H CH3 -C3H7(n) m.p. 137-138C

1.010 ,¢~1~ H CH3 -Cl-I(C~I3)2 1.011 ,¢~1' H -CH3 ~ m.p. 1()4-1()6C

1.012 ,¢~/ H -CH3 {~ > m.p. 146- 147~C

2 ~ 3 1 Comp. A Rl R2 R3 Phys. data No.

1.013 ~/ H -CH3 ~ m.p. 146-149C

1.014 ,¢~1~ H -CH3 --CH2 ~ m.p. 116-118C

1.015 ,¢~1' H -C2Hs -CH3 1.016 ,¢~1~ H -C2Hs -CH2CH3 m.p. 113-114C

1.017 ,~/ H -C2Hs -C3H7(n) 1.018 ,¢~ H -C2Hs -CH(CH3)2 1.019 ~/ H -C2Hs ~1 1.020 ,¢;~1' H -C2Hs {~3 1.021 ,¢;~/ H -C2}Ts 1.022 ,¢~/ H -C2Hs --CH

1.023 ,¢~/ H -C3H7(n) -CH3 1.024 ,¢~1~ E-I -C3H7(") -C2Hs ~ ~ 5 ~

Comp. A Rl R2 R3 Phys. data No.

1.025 ,¢~/ H -C3H7(n) -C3H7(n) m.p. 112-113C

1.026 ,¢;~/ H -C3H7(n) -Cll(CH3)2 1.027 ,¢~/ H -C3H7(n) ~

1.028 ,¢;~1' H -C3H7(n) {~3 1.029 ,¢;~)/ H -C3H7(n) 1.030 ,¢~1~ H -C3H7(n) _CH

1.031 ,¢;~/ H -CH(CH3)2 -CH3 1.032 l!~ J H -CH(CH3)2 _~2Hs 1.033 J!~ J H -CH(CH3)2 -C3H7(n) 1.034 ,¢;~ H -CH(CH3)2 -CH(CI-I3)2 1.035 ,¢~ H -CH(CI-I3)2 <I

1.036 J~ H -CH(CH3)2 ~3 2~527~

Comp. A Rl R2 ~3 Phys. data No.

1.037 ,¢~1' H-CH(C~I3) 1.038 ,¢~ -CH(CH3)2 --CH

1.039 ,¢~1/ H <1 CH3 1.040 ,¢~J~ H <1 -C2Hs m.p. 115-116C

1.041 ,¢~J~ H ~ -C3H7(n~

1.042 ,¢~/ H ~ -CH(CH3)2 1.043 ,¢~ H <1 ~

1.044 ,¢~1' H ~ {~3 1.045 ,¢~1' H

1.046 ,¢~1' H--~ --Cl1 1.047 ,¢;~1' 11 H -CH3 ~27 Comp. A Rl R2 R3 Phys. data No.
_ . _ _ . . .. _ 1.048 ,~ H H -C2Hs Cl N

1.049 J~ H H -C3H7(n) o 1.050J~ H H -CH(CH3)~
Cl N

1.051,¢~ H H

o 1.û52 ,¢~ H H {~3 o 1.053 ,¢~ H H

1.054J~ H H --CH
o 2 ~

Comp. A Rl R2 R3 Phys. data No.

Cl J~ H CH3 -CH3 1.056,¢~ E-I CH3 -C2fls m.p. 152-155C

1.057,1~ H CH3 -C3H7(n) m.p. 117-121C

1.058,¢;~ H CH3 -CH(CH3)2 m.p. 138C
o 1.059 ,¢~ H CH

o 1.060 ,¢;~ H CH3 {~3 m.p. 153C

1.061 ,1~ H CH3 ~

7 3 ~

Comp. A Rl R2 R3 Phys. data No.

1.062 ,¢~ H CH3 --CH

o 1.063 ,¢~ H ~ -CH3 1.064 ,¢~ H ~ -C2H5 o 1.065 ,¢~ H<1 -C3H7(n) 1.066 ,¢;~ H ~ -CH(CH3)2 1.067 ,¢~ H<1 <I
o 1.068 ,¢~¦~ H ~ { 3 o 2~2~3~

Comp. A Rl R2 R3 Phys. data No.
_ _ _ 1.0~9 ~ H ~ ~
r 1.070 ~ H ~ - CH

1.071 ~ H H -CH3 1.072 ~ H H ~2Hs 1.073 ~ H H -C3H7(n) 1.074 ~ H H -CH(CH3)2 1.075 ~ H H

1.076 ~ H H

1.077 ~ H H

3 ~

Comp. A ~ R2 ~3 Phys. data No.
_ _ 1.078 ~ H II --CH

1.079 )~/ H CH3 -CH3 1.080 )~/ H CH3 -C2Hs 1.081 ~/ H CH3 -C3H7(n) 1.082 ~ H CH3 -CH(CH3)2 1.083 )~/ H CH3 --<

1.084 ~/ H CH3 1.085 ~/ H CH

1.086 )~/ H CH3 --CH

1.087 ~/ H ~ -CH3 3 :~

Comp. A Rl R2 R3 Phys. data No.

1.088 ~/ H~ -C2Hs 1.089 ~ H~ -C3H7(n) 1.090 ~/ H~ -CH(CH3)2 1.091 ~/ H~ ~

1.092 ~ H~ { 3 1.093 ~ H<

1.094 ~/ H<1 --CH

1.095 CIJ~3~ H H -C2Hs N
1.096 Cl~ H H -C3H7(n) N

1.097 Cl~ H H -CH(CH3)2 1.098 Cl~ H H --1.099 CIJ~ H H {~

3 ~

Comp. A Rl R2 R3 Phys. data No.

1.100 Cl~l~ H H

1.101 Cl~3~ H H --CH

1.102 Cl1~3~ H CH3 -CH3 1.103 Cl~ H CH3 -C2H5 1.104 Cl~ H CH3 -C3H7(n) amorphous 1.105 Cl~ H CH3 -CH(CH3)2 1.106 CIJ~ H CH3 ~1 1.107 Cl~3~ H CH3 {~3 1.108 CIJ~]~ H CH

1.109 CIJ~ H CH3 --CH

1.110 Cl~ H ~ -CH3 1.111 CIJ~3~ H ~ -C21 15 1.112 Cl~ H ~ -C3H7(n) 1.113 ClJ~ H ~ -CII(C~I3)2 1.114 Cl~l~ H ~ ~

1.115 Cl~]~ H ~ {~3 2~5~

Comp. A Rl R2 R3 Phys. data No.

1.116 C~ ~ H ~ --N

1.117Cl~ 3~ H ~ --C

1.118 ¢~ H H -CH3 b 1.119 ¢~ H H -C2Hs o 1.120 ¢~ H H -C3H7(n) o 1.121 ¢~ H H -CH(CH3)2 o 1.122 ¢~ H H
b 1.123 ¢~ H H {~>

1.124 ¢;~ H H

1.125 ¢~ H H --CH~

2~2~ ~

Comp. A Rl R2 R3 Phys. data No.
_ 1.126 ¢~ H H -CH3 1.127 ¢~ H CH3 -C2Hs 1.128 ¢~ H CH3 -C3H7(n) amorphous mass 1.129 ¢~ H CH3 -CH(CH3)2 1.130 ¢~ H CH3 ~ m.p. 18S~C

1.131 ¢;~ H CH3 {~3 1.132 ¢~ H CH

1.133 ¢~ H CH3 --CH

2~73~

Comp. A Rl R2 R3 Phys. data No.

1.134 ¢~ CH3 1.135 ¢~ I I~ -C2115 1.136 ¢~ H <1 -C3H7(n) 1.137 ¢~ H ~ -CH(CH3)2 1.13~ H ~1 <1 1.139 ¢;~ H ~ ~3 1.140 ¢~

1.141 ¢~ H ~ ~C~12-~

Comp. A Rl R2 R3 Phys. data No.

1.142 ¢~ H H -CH3 m.p. 142-144"C

1.143 ¢~ H -C~I3 -CH3 1.144 ¢;~ H -~ -CH3 1.145 ¢~ H H -C2Hs 1.146 ¢~ H -CH3 -C2H5 1.147 ¢;~ H <1 -C2Hs 1.148 ,¢~ H --CH2 ~ -C3H7(n) m.p. 127-129C

1.149 ,¢~ H - CH2~ -C3H7(n) 1.150 ,¢~ H - CH2~=~ Cl -C31-17(n) 1.151 ,¢~ H --CH2 ~ -C3H7(n) 1.152 ,¢;~ H --CH2 ~ ~

2 ~

- 4~ -Comp. A Rl R2 R3 Phys. data No.
_ 1.153 ~¢~ H -CH2~CI <1 m.p. 190-192C

1 lSa, ,¢~ H -CH2~ --<1 1.155 ,¢~ H H -CH2COOCH3 m.p. 184-186C

1.156 ,~ H CH3 -CH2COOCH3 m.p. 185C

1.157 ,¢~ H ~ -CH2COOCH3 1.158 Cl~L H H -~H2COOCH3 N
1.159 CIJ~s~ H CH3 -CH2COOCH3 1.160 cl~L H ~ -CH2COOCH3 1.161 ,1~ H H -CH2COOCH3 1.162 ,¢~ H CH3 -Cl-12COOCI-13 r ~2~

Comp. A Rl R~ R3 Phys. d~ta No.
_ _ _ 1.163 ,¢~ H ~ -CT I2COO('H3 ~/ H 11 -CIIzCOOCHl 1.165 ¢;~ H CH3 -CH2COOCH3 1.166 ¢~ H ~ -CH2COOCH3 1.167 ~ H H -CH2COOCH3 1.168 ~ H CH3 -Cl12COC)CI-1 1.169 ~ ~ Cl-12COOCfl 1.170 ,¢~ H CH3 -C112C~3 2 ~ 3 ~

Comp. A Rl R2 R3 Phys. data No.

1.171 J~ H CH3 -CH2CF3 1.172 ~ H CH3 -CH2CF3 1.173 C~ L H CH3 -CH2CF3 1.174 ¢~ H CH3 -CH2CF3 1.175 ,¢~ H CH3 -CH2CH2F

1.176 ,¢;~ H CH3 -CH2CH2F

1.177 ~ H CH3 -CII2CII2F' 1.178 CIJ~L H CH3 -cH2clI2F

1.179 ¢~ H CH3 -Cl12CH2F

2~273 ~

Comp. A Rl R2 R3 Phys. data No.

1.180 ,¢~ H CH3 -CH2CH2Br 1.181 ,¢~ H CH3 -CH2CH2Br 1.182 ~ H CH3 -CH2CH2Br 1.183 C~ L H CH3 -CH2CH2Br 1.184 ¢~ H CH3 -CH2CH2Br 1.185 J~ H CH3 -CH2CH2CH2cl 1.186 ,1~1' H CH3 -CH2CH2CH2CI

1.187 ~ H CH3 -CI-12CH2Cl-l2 1.188 ,¢~ H CH3 -CH2('l-l2Cl-2~273~

Comp. A Rl R2 R3 Phys. data No.
.. . . _ 1.189¢~ H CH3 -CH2CH2C~I2cl 1.190,¢~ H CH3 -CH2CH2CH2Br 1.191,¢~ H CH3 -CH2CH2CH2Br Cl~
1.192 J~ J H CH3 -CH2CH2CH2E~r N

1.193CI~L H CH3 -CH2CH2CH2Br 1.194¢;~ H CH3 -CH2CH2CH2Br 1.195,¢~ H CH3 -CH2CH2CI

1.196,¢;~ H CH3 -CH2CH2CI

Cl~
1.197 H CH3 -CH2CH2CI

~ ~ rV ~ 7 3 :L

- 50 - .

Comp. A Rl R2 R3 Phys. data No.
-1.198 C~ L H CH3 -CH2CH2CJ

1.199¢~ H CH3 -CH2CH2CI

1.200,¢~ H CH3 -CH2CH(Cl)CH2CH2CH2Cl 1.201,¢;~ H CH3 -CH2CH(CI)CH2CH2CH2Cl o 1.202~ H CH3 -CH2CH(Cl)CH2CH2CH2CI

1.203CIJ~L H CH3 -CH2CH(Cl)CH2CH2CH2Cl 1.204¢~ H CH3 -CH2CH(Cl)CH2CI-I2CH2CI

1.205,¢~ H CH3 -CH2CH20E:I amvrpho~ls mass 1.206,¢~ H CH3 -CH2CI-12OH

20~731 Comp. A Rl R2 R3 Phys. data No.

1.207~ H CH3 -CH2CH2OH

1.208C~ L H Cl13 -CH2CH2OH

1.209¢~ H CH3 -CH2CH20H

1.210,~ H CH3 -CH2CH2CH2OH amorphous mass 1.211,¢~ H CH3 -CH2CH2CH2OH

1.212~ H CH3 -CH2CH2CH2OH

1.213CIJ~L H CH3 -CII2CH2CH20H

1.214¢~ H CH3 -Cl-I2CI 12CH2OI 1 1.215,¢~ H CH3 -Cl12(cH2)2cI-I2O~l m.p. 108-110C

2~273~

Comp. A Rl R2 R3 Phys. data No.
_ _ 1.216 ,¢~ H CH3 -CH2(CH2)2CH2OIl 1.217 ~ H CH3 -CH2(CH2)2CH2OH

1.218 C~ L H CH3 -CH2(CH2)2CH20H

1.219 ¢~ H CH3 -CH2(cH2)2cH2OH
N

1.220 ,¢~ H CH3 -CH2(CH2)3CH20H

1.221 ,¢~ H CH3 -CH2(CH2)3CH20H

1.222 ~ H CH3 -CH2(cH2)3c~I2O

1.223 Cl~ H CH3 -CH2(CH2)3~ 2O~

1.224 ¢~ H CH3 -CE-I2(CE-I2)3CI-12o~ 1 2 0 .~ 2 7 3 ~

Comp. A Rl R2 R3 Phys. data No.
____ 1.225 ,¢~ H CH3 -CH(CH3)CH2OH amorphous mass 1.226 ,¢~ H CH3 -CH(CH3)CE~20H
g 1.227 ~ H CH3 -CH(CH3)C~ 12CH

1.228 C~ L H CH3 -CH(CH3)CH20H

1.229 ¢ ~ H CH3 -CH(CH3)CH20H
N

1.230 ,1~ H CH3 -CH(C2Hs)CH20H

1.231 ,¢;~ H CH3 -CH(C2Hs)CH2QH

1.232 ~ H CH3 -CH(C2Hs)CH2Oll 1.233 Cl~ H CH3 -Cl-l(C2T-Is)CH201 I

2~27~1 Comp. A Rl R2 R3 Phys. data ._ _ ___ 1.234 ¢~ H CH3 -CH(C2Hs)CH2OH

1.235 J~ H CH3 -CH2CH(CH3)0H

1.23G ,¢~ H CH3 -CH2CH(CH3)0H

1.237 ~ H CH3 -CH2CH(CH3)OH

1.238 C~ L H CH3 -CH2CH(CH3)OH

1.239 ¢~ H CH3 -CH2CH(CH3)0H

1.240 ,¢~ H CH3 -CH2CH(OH)CH2OH

1.241 ,¢;~ H CH3 -CH2CII(OI-I)CH2OH

1.242 ~ H CH3 -CH2C~-I(OI-I)CH2OH

Comp. A R~ R2 R3 Phys. data No.
... _ _ .... . ... _ . .. _ . .

1.243 C~ L H CH3 -CH2CH(OH)CH2OI I

1.244 ¢~ H CH3 -CH2CI l(OI-l)CH2OI l 1.245 ,¢~ H CH3 -CH(CH2OI-I)2 1.246 ,¢;~1' H CH3 -CH(CH20H)2 1.247 ~ H CH3 -CH(CH2OH)2 1.248 Cl~ H CH3 -CH(CH2OH)2 1.249 ¢~ H CH3 -CH(CH20H)2 1.250 ,¢~ H CH3 -CH2CH20CH3 1.251 ,¢;~1~ H CH3 -Cl 12C~-120CI-13 ~2~

Comp. A Rl ~2 R3 Phys. data No.
_ _ _ 1.252 ~ H CH3 -Cl-12CI-I2OCH3 1.253Cll~ H CH3 -Cl~2CH20CI-I3 1.254 ~ H CH3 -CH2CH2OCH3 1.255 ~ H CH3 -CH2CH2CH2OC2Hs 1.256 ~ H CH3 -CH2CH2CH2OC2H5 1.257 ~ H CH3 -CH2CH2cH2OC2Hs 1.258Cll~ H CH3 -CH2CH2CH20C2H5 1.259 ~ H CH3 -CE-I2CH2c~l2OC2I-15 1.260 ~ H CH3 -Cl-I(CI-13)CI12OC H3 ~2~3~

Comp. A Rl R2 R3 Phys. data No.

1.261 ~ H CH3 -CH(CH3)CH20CH3 1.262 ~ H CH3 -CH(CH3)CH20CH3 1.263 Cll~ H CH3 -CH(CH3)CI 120CH3 1.264 ~ H CH3 -CH(CH3)CH20CH3 1.265 ~ H CH3 -CH2CH(OCH3)2 1.266 ~ H CH3 -CH2CH(OCH3)2 Cl N

1.267 ~ H CH3 -Cl-12CH(OCH3)2 1.268 Cll~ H CH3 -CH2CI-I(OCI-13)2 1.269 ~ H CH3 -Cl l2CI l(OC113)2 N

2 ~ ~' 2 r7 ~ ~

Comp. A Rl R2 R3 Phys. data No.
. . .

1.270~ H CH3 -CH2CH(OC2~ls)2 1.271~ H CH3 -CH2CH(OC2~ls)2 1.272~ H CH3 -CH2CH(OC2lIs)2 1.273Cll~ H CH3 -CH2CH(OC2Hs)2 1.274~ H CH3 -CH2CH(OC21I5)2 1.27~~ H CH3 -CH2CH2N(CH3)2 1.276~ H CH3 -CH2CH2N(CH3)2 1.277~ H CH3 -CH2CH2N(Cl-l3)2 N

1.278 Cll~ H CH3 -Cl-12Cl 12N(CI 13)2 2 ~ ~ 2 ~ 3 Comp. A Rl R2 R3 Phys. data No.

1.279 ~ H CH3 -CH2CH2N(CH3)2 1.280 ~ H CH3 -CH2CH2N(C2Hs)2 1.281 ~ H CH3 -CH2CH2N(C2Hs)2 1.282 ~ H CH3 -CH2CH2N(C2Hs)2 1.283Cll~ H CH3 -CH2CH2N(C2Hs)2 1.28~ ~ H CH3 -CH2CH2N(C2~Is)2 N

1.285 ~ H CH3 -CH2CH2CH2N(CH3)2 1.286 ~ H CH3 -CH2CH2CH2N(CH3)2 o 1.287 ~ H CH3 -CH2CH2CH2N(CH3)2 2~5~731 Comp. A Rl R2 R3 Phys. data No.
N

1.288CIJ~L H CH3 -CH2CH2CH2N(cH3)2 1.289 ¢~ H CH3 -Cf-12CH2Cf I2N(CH3)2 1.290,¢~ H CH3 -CH2CH2CH2N(C2Hs)2 1.291,¢~1' H CH3 -CH2CH2CH2N(C2Hs)2 ~r .
Cl~
1.292)~ J H CH3 -CH2CH2CH2N(C2Hs)2 1.293Ci~L H CH3 -CH2CH2CH2N(C2Hs)2 1.294 ¢~ H CH3 -CH2CH2CH2N(C2Hs)2 1.295,~ H CH3 -~H2COOC2Hs alIIorpllous mass 1.296,¢~ H CH3 -CH2COOC2Hs 2~2t~3,~

Comp~ A Rl R2 R3 Phys. data No.

1.297~ H Cl-13 -cH2cooc2Hs 1.298Cll~ 11 CH3 -Cl-12cOOc2f-ls 1.299~ H CH3 -CH2COOC2l ls 1.300~ H CH3 -CH2CH2COOC2Hs m.p.78-80C

1.301~ H CH3 -CH2CH2COOC2H5 1.302~ H CH3 -CH2CH2COOC2Hs 1.303Cll~ H CH3 -CH2CH2COOC2H5 1.304~ H CH3 -CH2cH2cOoc2~s 1.305~,~ H CH3 -Cll(CH3)C1-l2cOOc2l-l5 20~273~

Comp. A Rl R2 R3 Phys. data No.

1.306 ,1~ H CH3 -Cll(CI-I3)CH2COOC2Hs Cl~
1.307 J~ ~J H CH3 -CH(CH3)CH2COoc2~ls N

1.308CI~L H CH3 -CH(CH3)CH2COOC2H5 1.309 ¢~ H CH3 -CH(CH3)CH2cOoc2Hs 1.310,~ H CH3 -CH(CH2OH)COOCH3 1.311,¢~1' H CH3 -CH(CH2OH)COOCH3 Cl~
1.312,,l~ ,J ll CH3 -CH(CH2OH)COOCII3 1.313CIJ~ H CH3 -Cl-l(CH2OH)COOCH3 1.314 ¢~ H Cl 13 -Cl-l(CI-12OI-l)COOCI 13 N

2~73~

Comp. A Rl ~2 R3 Phys~ data No.
. _ 1.315~ H CH3 -Cl ~N {~

1.317~ H CH

1.318 Cll~ H CH

1.319~ H CII3 ~

1.320Cl~ H CH3 ~ m.p.137-139C
(cis isomer) m.p.170-172C
(trans isom~r) 1.321~ H CH3 - ~C~i3 o 1.322~ H CII3 ~CI~3 1.323Cll~ H CH3 ~ C~13 2 ~ ~ 2 7 ~ 1 Comp. A Rl R2 R3 Phys. data No.
_ 1.324 ~ H CH3 ~ CH3 1.325 ~ H CH3 CH3 1.326 ~ H CH3 CH3 1.327 ~ H CH3 CH3 1.328 Cll~ H CH3 CH3 1.329 ~ H CH3 CH3 1.330 ~ H CH

1.331 ~ H CH

2 ~ ~ ~ 7 3 ~

Comp. A Rl R2 R3 Phys. data No.

1.332 ~ H CH3 ~>

1.333 CIJ~L H CH3 ~>

1.334 ¢;~ H CH3 ~>

1.335 ,¢~ - H CH3 -CH2CH=CH2 m.p. 75-77C

1.336 J~ lH CH3 -CH2CH=CH2 1.337 ~ H CH3 -CH2CH=CH2 1.33~ CIJ~L H CH3 -CH2CH=Cf 12 1.339 ¢~ H CH3 -CH2CH=Cl-l2 1.340 ,¢~ H CH3 ~ Cl 2 0 ~ 2 ~ 31 Comp. A Rl R2 R3 Phys. data No.
_ _ _ _ 1.341 ,¢~ H CH3 ~ Cl 1.342 ~ H CH3 ~ Cl 1.343 CIJ~L H CH3 ~ Cl 1.344 ¢~ H CH3 ~ Cl 1.345 ,~ H CH3 ~ F amorphous mass 1.346 ,¢~f H CH3 ~ F

1.347 ~ H CH3 ~ F

1.348 CIJ~L H CH3 --~ F

3 ~

Comp. A Rl R2 R3 Phys. data No.

1.349¢~ H CH3 ~ F

1.350,¢~ H CH3 ~OCH3 m.p. 204C

1.351,¢~ H CH3 ~ OCH3 o 1.352~ H CH3 ~ OCH3 1.353CI~L H CH3 ~ OCH3 1.354¢~f H CH3 ~ OCH3 1.355,¢~ H CH3 ~ CH3 amorphous m.lss 1.356,¢;~ H CH3 ~~ C~13 ~0 1.357~ H CH3 ~ C~13 s~ j 3 ~

Comp. A ~l R2 R3 Phys. data No.
-1.358 C~ L H CH3 ~ CH3 1.359 ¢~ H CH3 --~ CH3 1.360 ,¢~ H CH3 ~N02 m.p. 219C

1.361 ,¢~ H CH3 ~ NO2 o 1.362 ~ H CH3 ~ NO2 1.363 C~ L H CH3 ~ NO2 1.364 ¢;~ H CH3 ~ N02 1.365 ,¢~ H CH3 ~ CN .Imorpholls mass 1.366 ,¢~ H CH3 ~ CN

2~2731 Comp. A Rl R2 R3 Phys. data Ns~.

1.367 ~ H CH3 ~ CN

1.368 CI~L H CH3 ~ CN

1.369 ¢~f H CH3 ~ CN

1.370 J~ H CEI3 ~ CF3 amo~phous mass 1.371 ,1~ H CH3 ~CF3 1.372 ~ H CH3 ~ CF3 1.373 Cl~ H CH3 ~ CF3 1.374 ¢~ H CH3 ~ CF3 1.375 ,¢~f H CH3 ~

2 ~ ~ 2 7 3 ~

Comp. A Rl R2 R3 Phys. data No.

1.376 J~ H CH3 1.377 ~ H CH

1.378 CIJ~L H CH
S

1.379 ¢~ HCH3 ~

1.380 ,¢;~ HCH3 SCH3 1.381 ,¢~1' HCH3 SCH3 Cl~ SC~13 Cl~ NJ 3 ~

1.383 CI~L H CH3 ~

~52~3~

Comp. A Rl R2 R3 Phys. data No.
. . . _ 1.384 ¢;~ H CH3 SC~3 1.385 ,¢~ H CH3 Cl 1.386 ,¢~ H CH3 Cl o Cl Cl 1.387 ~ H CH

1.388 C~ L H CH

1.389 ¢~ H CH

1.390 ,¢~ H CH3 CN

1~391 ,¢~ H Cl13 CN

~O~

~2~31 Comp. A Rl R2 R3 Phys. data No.
.

1.392~ H CH3 CN

1.393 CI~L H CH

1.394¢~ H CH3 ~

1.395,~ H CH3 -CH2~ N2 amorphous mass 1.396,¢~ H CH3 -CH2~ N2 ~0 1.397~ H CH3 -CH2~ No2 1.398CI~L II CH3 -CH2~ N2 1.399¢~ H CH3 -CH2~ N2 o 1.400,¢~ H CH3 -CH2~ F m.p. 162-164C

2~2~

Comp. A Rl R2 R3 Phys. data No.

1.401J~ H CH3 -CH2~ F

~0 1.402 ~ H CH3 -CH2~ F

1.403c~ L H CH3 -CH2~ F

1.404¢;~ H CH3 -CH~ F

1.405,¢~ H CH3 -CH2~0CH3 m.p. 125-127C

1.406,¢;~ H CH3 -CH2~ OCH3 ~0 1-407Cl~¢N~ H CH3 -CH2~ OCH3 1.408 C~ L H CH3 -CH2~ OCH3 7 3 ~

Comp. A Rl R2 R3 Phys. data No.

1.409 ¢~ H CH3 -CH2~ oc~l3 1.410 ,~ H CH3-CH2~CI m.p. 147-149C

1.411 ,¢;~ H CH3-CH2~ Cl o 1.412 ~ H CH3-CH2~ Cl 1.413 Cl l~L H CH3-CH2~ Cl 1.414 ¢~ H CH3-CH2~ Cl 1.415 ,¢~ H CH3-C112 ~CH3 m.p. 155-157C

1.416 '~?' H CH3 -CH2 ~C~13 7 3 ~

Comp. A Rl R2 R3 Phys. data No.

1.417 ~ H CH3 -CH2 ~CH3 1.418 Cll~ H CH3 -CH2 ~CH3 1.419 ~ H CH3 -CH2 ~ CH3 1.420 ~ H CH3 -CH2 ~CF3 m.p. 167-169C

1.421 ~ H CH3 -CH2 ~ CF3 1.422 ~ H CH3 -CH2 ~CF3 1.423 Cll~ H CH3 -CH2 ~CF3 1.424 ~ H CH3 -C~12 ~CF3 ~0 1.425 ~ H CH3 -CH2 ~

~ ~ ~ rJ 7 ~ ~

Comp. A Rl R2 R3 Phys. data No.
.... . _ _ .

1.426 ,¢;~ H CH3 -CH

o 1.427 ~ H CH3 -CH

1.428 C~ L H CH3 -CH2 ~

1.429 ¢~ H CH3 -CH

1.430 ,¢~ H CH3 -CH

1.431 ,¢~1' H CH3 -CH

F

1.432 ~ H CH3 -CH

~a27~ lL

Comp. A Rl R2 R3 Phys. data No.

1.433 CI~L H CH3 -CH

1.434 ¢~ H CH3 -CH2 ~

1.435 ,~ H CH3 -CH2 ~ F

1.436 ,¢~ H CH3 -CH2 ~ F

o 1.437 ~ H CH3 -CH~---~ F

1.438 C~ L H CH3 -CH2 ~ F

1.439 ¢~f H CH3 -CH2--~ F

2~ '3~

Comp. A Rl R2 R3 Phys. data No.
.
CN
1 440 ,¢~ 11 CH3 -CH2 ~
CN
1.441 ,¢~ H CH3 -CH2 ~
o CN

1.442 ~ H CH3 -CH2 ~

CN
N /~
1.443 C~ L H CH3 -CH2 ~
CN

1.444 ¢~ H CH3 -CH2 ~

1.445 ~ H CH3 -C3117(n) m.p. 157-158C
C N

o ~5~ ~'3:~

Example 3:

Formulations (throughout, percentages are by weight) Example F1: Emul~sifiable concentrates a~ b~ c) a compound of Example 2 25 %40 % 50 %
calcium dodecylbenzenesultonate 5 %8 % 6 %
castor oil polyethylene glycol ether (36 mol of ethylene oxide~ 5 %
tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12 % 4 %
cyclohexanone - 15 % 20 %
xylene mixture 65 %25 % 20 %

Emulsions of any desired concentration can be produced from such concentrates bydilution with water.

ExampleF2: Solutions a) b) c) d) a compound of Example 2 80 %10 %5 % 95 %
ethylene glycol monomethyl ether 20 % - - -polyethylene glycol (mol. wt. 400) - 70 %
N-methyl-2-pyrrolidone - 20 %
epoxidised coconut oil - - I % 5 %
petroleum fraction (boiling range 160-190C) - - 94 %

The solutions are suitable for application in the torm of micro-drops.

_ampleF3. Granules a) b) c) d) a compound of Example 2 5 % 10 %X % 21 %
kaolin 94 % ~79 % 54 %
highly dispersed silicic acid I % - 13 % 7 %
attapulgite - 90% - 18 %

3 ~

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

ExampleF4. Dusts a)b) a compound of Example 2 ~ %5 %
highlydispersedsilicic acid 1 %S %
talcum 97 %
kaolin - gO %

Ready-for-use dusts are obtained by intimatcly mixing the calTiers with the active ingredient.

Example F5: Wettable powders a)b) c) a compound of Example 2 25 %50 % 75 %
sodiumlignosulfonate 5 %5 %
sodium laurylsulfate 3 % - 5 %
sodium diisobutylnaphthalene-sulfonate - 6 % 10 %
octylphenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 %
highly dispersed silicic acid 5 %10 % 10 %
kaolin 62 %27 %

The active ingredient or active ingredient combination is mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsifiable concentrate a compound of Example 2 1 () %
octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 %
calcium dodecylbenzenesulfon"te 3 %
castor oil polyglycol ether (36 mol of ethylene oxide) 4 %
cyclohexanone 3() %

2~2~3 ~

xylene mixture 50 %

Emulsions of any desired concentration can be obtained from this concentrate by dilution with water.

ExampleF7: Dusts a) b) a compound of Example 2 S %8 %
talcum 95 %
kaolin - 92 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable rnill.

Example F8: Extruder ~ranules a compound of Example 2 10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %

The active ingredient or active ingredient combination is mixed and ground witn the adjuvants, and the mixture is moistened with water. The mixture is extruded, granulated and then dried in a stream of air.

Example F9: Coated ~ranules a compound of Example 2 3 %
polyethylene glycol (mol. wt. 200) 3 %
kaolin 94 %

The finely ground active ingredient or active ingreclient combin;ltion is unitormly applie(l, in a mixer, to the kaolin moistened with polyethylenc glycol. Non-dusty coated gl,lllllles are obtained in this manner.

Example F10: Suspension concentrate a compound of Example 2 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
silicone oil in the form of a 75 %
aqueous emulsion 1 %
water 32 %

The finely ground active ingredient or active ingredient combination is intimatcly mixed with the adjuvants, giving a suspension concentrate from which suspensions of .my desired concentration can be obtained by dilution with water.

Example 4: Action a~ainst Nilaparvata lu~ens Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound.
After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is detennined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.

Compounds of Example 2 exhibit good activity against Nilaparvata lugens in this test. In particular, compounds 1.007, 1.008, 1.009, l.S)11, 1.012, 1.013, 1.014, 1.056, 1.057, 1.058, 1.104, 1.128, 1.130, 1.156, 1.205, 1.215, 1.300, 1.320, 1.335 and 1.410 are more than 80-90 % effective.

Example 5: Action against Nephotettix cincticeps Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound.
After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparin~ the nurmber of surviving cicad.ls on the treated plants with that on untreated phlnts.

Compounds of Example 2 exhibit good aclivity ag,linst Ncphotettix chlcticcps hl tllis ~est.
Inparticular,compounds 1.007, 1.0()8, 1.009, 1.()11, 1.()12, 1.013, 1.()14, 1.()56, 1.()57, 1.058, 1.060, 1.104, 1.128, 1.156, 1.205, 1.215, 1.30(), 1.320, 1.335 alld 1.410 are more than 80 % effective.

2~ 2~3 L

Example 6: Action a~ainst Myzus persicae Pea seedlings are infested with My~us persicae and then sprayed with a spray mixture comprising 400 ppm of the test compound, and incubated at 20C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on wnlreated plants.

Compounds of Example 2 exhibit good activity against Myzus persicae in this test. In particular, compounds 1.001, 1.002, 1.006, 1.007, 1.008, 1.009,1.0] 1, 1.()12, 1.104 and 1.156 are more than 80 % effective.

Example 7: Action a~ainst APhis craccivora Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture comprising 400 ppm of the test compound, and incubated at 20C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.
.

Compounds of Example 2 exhibit good activity against Aphis craccivora in this test. In particular,compounds 1.001, 1.002, 1.006, 1.007, 1.008, 1.009, 1.011, 1.012, 1.104, 1.155, 1.156, 1.205 and 1.300 are more than 80 % effective.

Example 8: Systemic acti n a~ainstNilaparv_talu~ens Pots containing rice plants are placed in an aqueous emulsion solution comprisin~
400 ppm of the test compound. The rice plants are then populated with larvae in tlle 2nd and 3rd stages. Evaluation is made 6 days later. The percentage reduction in thepopulation (% activity) is determined by comparing the number of cicadas on the treate(l plants with that on untreated plants.

Compounds of Example 2 exhibit good acLivity against Nilap.lrvat.l lwgcns in this tcst. In particul.u, compounds 1.001, 1.002, 1.0()3, 1.()04, 1.006, 1.007, 1.008, 1.009, 1.()11, 1.()12, 1.013, 1.014, 1.057, 1.058, 1.060, 1.104, 1.12X, 1.13(), 1.142, 1.156, 1.2()5, 1.215, 1.3()(), 1.320, 1.335, 1.410 and 1.445 are more th;ln ~() % effcctive.

Example 9: Systemic action a~ainst Nephotettix cincticeps Pots containing rice plants are placed in an aqueoLIs emulsioll solution comprisin~
400 ppm of the test compownd. The rice plants are tllen popul.llcd with larvae in tlle 2nd and 3rd stages. EvaluaLion is made 6 days latel. The pcrcent.lge reduction in the 2 ~ 3 ~

population (% activity) is determined by comparing the number of cicadas on the treated plants with that on untreated plants.

Compounds of Example 2 exhibit good activity against Nephotettix cincticeps in this test.
In particular, compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.008, 1.009, 1.011, 1.012, 1.013, 1.014, 1.057, 1.058, 1.060, 1.104, 1.156 and 1.335 are more than ~() 'J/o effective.

Example 10 Systemic action again~t Mvzus persica_ Pea seedlings are infested with My~us persicae and ~hen placed with their roots in a spray mixture comprising 400 ppm of the ~est compound, and incubated at 20C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.

Compounds of Example 2 exhibit good activity against Myzus persicae in this test. In particular, compounds 1.001, 1.002, 1.007, 1.008, 1.009, 1.011, 1.012, 1.025, 1.104 and 1.156 are more than ~0 % effective.

Example 11: Action a~ainst Bemisia tabaci Dwarf bean plants are placed in gauze cages and populated with adults of Bemisia tabaci (whitefly). When oviposition has taken place, all the adults are removed and 10 days later the plants and the nymphs located thereon are sprayed with an aqueous emulsion of the test compounds (concentration 400 ppm). Evaluation is made 14 days after application of the test compound by deterrnining the % hatching rate in comparison with untreated controls.

Compounds of Example 2 exhibit good activity against Bemisia tabaci in this test. In particular,compounds 1.001, 1.002, 1.006, 1.007, 1.008, 1.()()9, l.011, 1.012, 1 013, 1.1)14, 1.016, 1.104, 1.156 and 1.335 are more than ~0 % cffective.

Example 12: Action a~ainst Ctenocepllal;ls felis 20 to 25 cat ilea eggs (Ctenocephalus felis) ~ure placed in each of a number of horizont.ll 50 ml cell culture bottles into which lS g of a flea larv.le nutrient medium comprising 100 ppm of the test compound have been introduced beforehand. The bottles .ure sealed and placed in an incubator at 26-27C and 60-70 % humidity. After an incubation period ~273~

of 21 days, the development of adult fleas, unhatched pupae ~nd larvae is assessed.

Compounds of Example 2 exhibit good activity in this test. In particular, compounds 1.009 and 1.025 are more than 80 % effective.

Exam~ Action against Blattella ~ermanica An amount of a 0.1 % solution of the test compound in acetone sufficient to produce a concentration of 1 g/rrl2is introduced into a petri dish having a diameter of 1() cm. When the solvent has evaporated, 10 Blattella germanica nymphs (final nymph stage) are placed in the dish so prepared and subjeeted to the action of the test compound for 2 hours. The nymphs are then narcotised with carbon dioxide, placed in a fresh petri dish and kept in the dark at 25C and about 70 % humidity. The insecticidal action is evaluated 48 hours later by determining the mortality rate.

Compounds of Example 2 exhibit good activity in the above test. In particular, compound 1.104 is more than 60 % effective.

Example 14: Action against Boophilus microplus Adult female ticks which are replete with blood are affixed to a PVC plate and covered with a cotton wool swab. For treatment, 10 rrll of an aqueous test solution comprising 125 ppm of the test compound are poured over ~he test insects. The cotton wool swab is then removed and the ticks are incubated for 4 weeks until oviposition has taken place.
The action against Boophilus microplus manifests itself either as mortality or sterility of the females or as ovicidal action in the eggs.

Compounds of Example 2 exhibit good activity against Boophilus microplus. In particular, compounds 1.008, 1.009 and 1.025 are more thall 60 % effective in this test.

Claims (53)

1. A compound of formula I

(I) wherein R1 is hydrogen or C1-C4alkyl;
R2 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl or a radical -CH2B;
R3 is hydrogen; C1-C10alkyl; C3-C6cycloalkyl; C1-C10alkyl substituted by from 1 to 12 radicals from the group halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9 halogen atoms, di-(C1-C4alkyl)amino and C1-C5alkoxycarbonyl;
C3-C6cycloalkyl substituted by from 1 to 4 C1-C4alkyl radicals or halogen atoms;C2-C8alkenyl or C2-C8alkynyl; C2-C8alkenyl or C2-C8alkynyl each of which is substituted by from 1 to 6 halogen atoms; phenyl; benzyl; or phenyl or benzyl each of which is substituted by from 1 to 3 ring substituents from the group halogen, C1-C4alkyl, C1-C4haloalkyl having from 1 to 9 halogen atoms, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9 halogen atoms, C1-C4alkylthio, nitro and cyano;

A is an unsubstituted or mono- to tetra-substituted aromatic or non-aromatic, monocyclic or bicyclic hetercyclic radical that can have one or two substituents from the group C1-C3haloalkyl having from l to 7 halogen atoms, cyclopropyl, halocyclopropyl having from 1 to 3 halogen atoms, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1 to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and from one to four substituents from the group C1-C3alkyl, C1-C3alkoxy and halogen; and B is phenyl; cyanophenyl; nitrophenyl; halophenyl having from 1 to 3 halogen atoms;

phenyl substituted by C1-C3alkyl, C1-C3haloalkyl having from 1 to 7 halogen atoms, C1-C3alkoxy or by C1-C3haloalkoxy having from 1 to 7 halogen atoms; 3-pyridyl;
5-thiazolyl; 5-thiazolyl substituted by one or two substituents from the group C1-C3alkyl, C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxy, C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1 to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy,halo-allylthio, halogen, cyano and nitro; or 3-pyridyl substituted by one or two radicals from the group C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3-haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or by from one to four radicals from the group C1-C3alkyl, C1-C3alkoxy and halogen;

or a salt thereof with an inorganic acid.

2. A compound of formula I according to claim 1 wherein R3 is C5-C10alkyl;
C3-C6cycloalkyl; C1-C10alkyl substituted by from 1 to [2 radicals from the group halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9 halogen atoms, di-(C1-C4-alkyl)amino and C1-C5alkoxycarbonyl; C3-C6cycloalkyl substituted by from 1 to 4 C1-C4-alkyl radicals or halogen atoms; C2-C8alkenyl or C2-C8alkynyl; C2-C8alkenyl or C2-C8alkynyl each of which is substituted by from 1 to 6 halogen atoms; phenyl; benzyl;
or phenyl or benzyl each of which is substituted by from 1 to 3 ring substituents from the group halogen, C1-C4alkyl, C1-C4haloalkyl having from 1 to 9 halogen atoms, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9 halogen atoms, C1-C4alkylthio, nitro and cyano; and R1, R2 and A are as defined in claim 1, or a salt thereof with an inorganic acid.

3. A compound according to either claim 1 or claim 2 wherein the hetelocyclic radical A
is unsaturated, is bonded via a carbon atom to the radical of the molecule of the compound of formula I and contains at least one nitrogen atom.

4. A compound according to claim 3 wherein the heterocyclic radical A is unsaturated, is bonded via a carbon atom to the radical of the molecule of the compound of formula I and contains from one to three hetero atoms from the group oxygen, sulfur and nitrogen, not more than one oxygen or sulfur atom being present.

5. A compound according to claim 4 wherein the heterocyclic radical A contains from one to three hetero atoms from the group oxygen, sulfur and nitrogen, of which one hetero atom is always nitrogen, not more than one oxygen atom or sulfur atom being present.

6. A compound according to either claim 1 or claim 2 wherein the heterocyclic radical A
is a heterocyclic basic structure, bonded via a carbon atom to the radical of the molecule of the compound of formula I, from the group , , and , which basic structure is unsubstituted or, depending on the number of substituents possible in the ring system, can carry up to four of the substituents defined in claim 1, and wherein E is C1-C3alkyl and Y is hydrogen, C1-C3alkyl or cyclopropyl.

7. A compound according to claim 6 wherein the heterocyclic radical A is unsubstituted or carries from one to three substituents from the group halogen, C1-C3alkyl, C1-C3haloalkyl and C1-C3haloalkoxy each having from 1 to 7 halogen atoms, and C1-C3alkoxy.

8. A compound according to claim 7 wherein the radical A is pyridyl or thiazolyl.

9. A compound according to either claim l or claim 2 wherein the radical B is a phenyl, pyridyl or thiazolyl radical each of which is unsubstituted or substituted d by one or two radicals from the group halogen, C1-C3alkyl, C1-C3haloalkyl and C1-C3haloalkoxy each having from 1 to 7 halogen atoms, and C1-C3alkoxy.

10. A compound according to claim 7 wherein the radical A is 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-4-yl, 1-oxopyrid-3-yl, 1-oxo-2-halopyrid-5-yl or 1-oxo-2,3-dihalopyrid-5-yl.

11. A compound according to either claim 1 or claim 2 wherein R1 is hydrogen, R2 is methyl, ethyl or cyclopropyl, and A is pyridyl, 1-oxopyridyl or thiazolyl, or pyridyl, 1-oxopyridyl or thiazolyl each of which is substituted by from one to three substituents from the group halogen, C1-C3alkyl, C1-C3haloalkyl and C1-C3haloalkoxy each having from 1 to 7 halogen atoms, and C1-C3alkoxy.

12. A compound according to either claim 1 or claim 2 wherein R1 is hydrogen.

13. A compound according to claim 12 wherein R1 is hydrogen and R2 is methyl.

14. A compound according to claim 1 wherein R3 is C1-C3alkyl, cyclopropyl, cyclohexyl, phenyl, benzyl or the radical -CH12-COO-CH3.

15. A compound according to claim 13 wherein R3 is benzyl substituted by from l to 3 ring substituents from the group fluorine, chlorine, bromine, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy, C1-C2alkylthio, nitro and cyano.

16. A compound according to claim 13 wherein R3 is benzyl substituted by from 1 to 3 ring substituents from the group fluorine, chlorine, bromine, C1-C2alkyl, C1-C2haloalkyl, C1-C2alkoxy, C1-C2alkylthio, nitro and cyano.

17. A compound according to claim 13 wherein R3 is C1-C6alkyl substituted by a hydroxy group.

18. A compound according to claim 13 wherein R3 is C1-C6alkyl substituted by a C1-C5alkoxycarbonyl group.

19. A compound according to claim 13 wherein R3 is -CH2CH2F, -CH2CH2Br, -CH2CH2CH2Cl, -CH2CH2CH2Br or -CH2CHCICH2CH2CH2Cl.

20. A compound according to claim 13 wherein R3 is -CH2CH2O-CH3, -CH2CH2CH2-O-CH2CH3, -CH(CH3)CH2-O-CH3, -CH2CH(OCH3)2, -CH2CH2-N(CH2CH3)2, -CH2-CH2CH2-N(CH3)2 or -CH2CH2CH2-N(CH2CH3)2.

21. A compound according to claim 13 wherein R3 is C4-C6cycloalkyl that is unsubstituted or substituted by one or two C1-C4alkyl radicals.

22. A compound according to claim 21 wherein R3 is cyclopentyl or cyclohexyl.

23. A compound according to claim 21 wherein R3 is C3-C6cycloalkyl substituted by one or two methyl groups.

24. A compound according to either claim 1 or claim 11 wherein A is 2-chlorothiazol-4-yl, 2,3-dichloropyrid-5-yl, 1-oxopyrid-3-yl or 1-oxo-2-chloropyrid-5-yl; R2 is methyl and R3 is cyclopropyl, -CH2CH2CI, -CH2CH(OCH3)2 or -CH2CH2N(CH3)2.

25. A compound according to claim 1 wherein A is 2-chlorothiazol-4-yl.

26. A compound according to claim 1 wherein A is 2-chloropyrid-5-yl.

27. A compound according to claim 1 wherein A is l-oxo-2-chloropyrid-5-yl or l-oxopylid-5-yl.

28. A compound according to claim 1 wherein A is 2-chloropyrid-5-yl, 2,3-dichloropyrid-5-yl, 2-chlorothiazol-4-yl, 1-oxopyrid-3-yl or 1-oxo-2-chloropyricl-5-yl;

R1 is hydrogen; R2 is methyl; and R3 is n-propyl.

29. A compound according to claim 26 of the formula .

30. A compound according to claim 26 of the formula .

31. A compound according to claim 26 of the formula .

32. A compound according to claim 26 of the formula .

33. A compound according to claim 26 of the formula

34. A compound according to claim 26 of the formula

35. A compound according to claim 26 of the formula

36. A compound according to claim 14 of the formula

37. A compound according to claim 14 of the formula

38. A compound according to claim 26 of the formula

39. A compound according to claim 25 of the formula

40. A compound according to claim 27 of the formula

41. A compound according to claim 14 of the formula

42. A compound according to claim 14 of the formula

43. A compound according to claim 14 of the formula

44. A compound according to claim 14 of the formula

45. A compound according to claim 26 of the formula

46. A compound according to claim 26 of the formula

47. A process for the preparation of a compound of formula I according to claim 1 (I) wherein R1 is hydrogen or C1-C4alkyl;
R2 is hydrogen, C1-C6alkyl, C3-C6cycloalkyl or a radical -CH2B;
R3 is hydrogen; C1-C10alkyl; C3-C6cycloalkyl; C1-C10alkyl substituted by from 1 to 12 radicals from the group halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkoxy having from 1 to 9 halogen atoms, di-(C1-C4alkyl)amino and C1-C5alkoxycarbonyl;
C3-C6cycloalkyl substituted by from 1 to 4 C1-C4alkyl radicals or halogen atoms;C2-C8alkenyl or C2-C8alkynyl; C2-C8alkenyl or C2-C8alkynyl each of which is substituted by from 1 to 6 halogen atoms; phenyl; benzyl; or phenyl or benzyl each of which is substituted by from 1 to 3 ring substituents from the group halogen, C1-C4aLkyl, C1-C4haloalkyl having from 1 to 9 halogen atoms, C1-C4,alkoxy, Cl-C4haloalkoxy having from 1 to 9 halogen atoms, C1-C4alkylthio, nitro and cyano;

A is an unsubstituted or mono- to tetra-substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyelic radical that can have one or two substituents from the group C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl having from 1 to 3 halogen atoms, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1 to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7 halogen aloms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and from one to four substituents from the group C1-C3alkyl, C1-C3alkoxy and halogen; and B is phenyl; cyanophenyl; nitrophenyl; halophenyl having from 1 to 3 halogen atoms;
phenyl substituted by C1-C3alkyl, C1-C3haloalkyl having frolll 1 to 7 halogen atoms, C1-C3alkoxy or by C1-C3haloalkoxy having from 1 to 7 halogen atoms; 3-pyridyl;
5-thiazolyl; 5-thiazolyl substituted by one or two substituents from the group C1-C3-alkyl, C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C1-C3alkoxy, C2-C3haloalkenyl and C2-C3haloalkynyl each having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1 to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, halo-allylthio, halogen, cyano and nitro; or 3-pyridyl substituted by one or two radicals from the group C1-C3haloalkyl having from 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3-haloalkynyl having from 1 to 4 halogen atoms, C1-C3haloalkoxy having from 1 to 7halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, or by from one to four radicals from the group C1-C3alkyl, C1-C3alkoxy and halogen;
or a salt thereof with an inorganic acid, which process comprises a) reacting a compound of formula II

(II) with formaldehyde, or paraformaldehyde, and a compound of formula III

H2N-R3 (III);
or b) reacting a compound of formula IV

(IV) with a compound of formula V

X-CH-A (V);
or c) for the preparation of a compound of formula I wherein R2 is other than hydrogen, reacting a resulting compound of formula I wherein R2 is hydrogen with a compound of formula VI

Y-R2 (VI);

and, if desired, converting a resulting compound of formula I into a salt thereof; R1, R2, R3 and A in formulae II to VI being as defined in claim 1, X being a halogen atom and Y
being a leaving group.

48. A compound of formula IV according to claim 47 (IV) wherein R2 and R3 are as defined in claim 1, with the exception of 2-nitroimino-5-methyl-1,3,5-triazacyclohexane and 2-nitroimino-1,3,5-triazacyclohexane.

49. A process for the preparation of a compound of formula IV according to claim 48, which comprises reacting a compound of formula VII

(VII) with formaldehyde, or paraformaldehyde, and a compound of formula III

H2N-R3 (III), R2 and R3 in formulae VII and III being as defined in claim 1.

50. A pesticidal composition comprising a compound according to claim 1 as active ingredient, together with suitable carriers and/or other adjuvants.

51. A method of controlling insects and representatives of the order Acarina, wherein the pests or their various development stages, or the locus thereof, are brought into contact or treated with a pesticidally effective amount of a compound of formula I according to claim 1 or with a composition comprising a pesticidally effective amount of such a compound together with adjuvants and carriers.

52. A method according to claim 51 for controlling plant-destructive insects.

53. A method according to claim 52 for controlling sucking insects.

FD 4.5